In this work, we present theoretical results in cyclic staircase voltammetry of a surface catalytic mechanism that features reversible chemical step, the so‐called “surface catalytic ECrev’ mechanism”. We consider specific surface regenerative mechanism, in which both of the electro‐inactive substrates are present in large excess in electrochemical cell from the beginning of the experiment. The chemical reversibility brings at this mechanism more complexity in respect to the features of well‐elaborated surface catalytic EC’ mechanism coupled with chemically irreversible regenerative reaction. As we present plenty of simulated cyclic voltammograms, we also propose methods to get insight to kinetics and thermodynamics parameters relevant to chemical regenerative step. The elaboreted results can be important in analysing the kinetics and thermodynamics of many drug‐drug and drug‐DNA interactions, for example. In addition, with the results elaborated in this work we can access relevant information about the chemistry of important lipophilic enzymes studied in protein‐film voltammetry set up.